One-dimensional nanostructures have attracted considerable attention due to their importance in basic scientific research and potential technologic applications. [1][2][3][4] Among them, vanadium pentoxide (V 2 O 5 ) nanowires have been extensively studied in recent years because of their prospective applications in chemical sensors, field-emitters, catalysts, lithium-ion batteries, actuators, and electrochromic or other nanodevices. [5][6][7] Several different approaches have been explored for the synthesis of V 2 O 5 nanowires, such as thermal evaporation methods, [8,9] hydrothermal/solvothermal syntheses, [5,10,11] sol-gel techniques, [12] and electrodeposition. [13] However, the nanowires synthesized by these methods have typical lengths in the micrometer range (most of them are shorter than 10 mm); moreover, if one can make centimeter-long V 2 O 5 nanowires, which should be much more useful compared to short wires for some specific purposes, such as field-emission (FE), device interconnects, and reinforcing fibers in composites. [14][15][16][17] Herein, we fabricated high-quality single-crystalline centimeter-long V 2 O 5 nanowires ($80-120 nm in diameter, several centimeters in length; aspect ratio >10 5 -10 6 ) using an environmental friendly hydrothermal approach without dangerous reagents, harmful solvents, and surfactants. The FE, electrochemical and electrical transport, and photoconductive properties of the synthesized V 2 O 5 nanowires were then investigated in detail. Our results suggest a high potential of utilizing these novel nanowires in field-emitters, lithium-ion batteries, interconnects, and optoelectronic devices.The representative morphologies of the V 2 O 5 nanowires were investigated by FE scanning electron microscopy (SEM), as shown in Figure 1a. Other SEM images (see the Supporting Information, Fig. S1) also confirm the high-yield fabrication of smooth and straight nanowires of $80-120 nm in diameter. Large portions of the nanowires are usually several millimeters or even up to several centimeters in length (inset of Fig. 1a), resulting in an aspect ratio of $10 5 -10 6. To the best of our knowledge, this is the first time that such ultra-long V 2 O 5 nanowires have been obtained. An X-ray diffraction (XRD) pattern of the sample is shown in Figure 1b Figure S2 (Supplementary Information) depicts a room temperature micro-Raman spectrum of the ultralong V 2 O 5 nanowires. The peaks, located at 145, 197, 285, 305, 407, 480, 525, 694, and 990 cm À1 , can be assigned to the Raman signature of V 2 O 5 . [18,19] A predominant low-wavelength peak at 145 cm À1 is attributed to the skeleton bent vibration (B 3g mode), while the peaks at 197 and 285 cm À1 derive from the bending vibrations of O C ÀVÀO B bond (A g and B 2g modes). The bending vibration of VÀO C (A g mode), the bending vibration of VÀO B ÀV bond (A g mode), the stretching vibration of VÀO B ÀV bond (A g mode), and the stretching vibration of VÀO C bond (B 2g mode) are regarded at about 305, 407, 525, and 694 cm À1 , respectively. Th...